热熔法预浸料用氰酸酯树脂的性能

霍肖蒙; 王帆; 姚卓君; 戴晶滨; 朱亚平; 齐会民

doi:10.13801/j.cnki.fhclxb.20200506.001

热熔法预浸料用氰酸酯树脂的性能

doi: 10.13801/j.cnki.fhclxb.20200506.001

霍肖蒙^1,,
王帆^1,,
姚卓君^2,,
戴晶滨^2,,
朱亚平^1,,
齐会民^1, ,

1.
华东理工大学　材料科学与工程学院特种功能高分子材料及其相关技术教育部重点实验室，上海 200237
2.
上海复合材料科技有限公司，上海 200120

基金项目: 上海航天科技创新基金（SAST2016120）；中央高校基本科研业务费专项资金（50321041918013；50321041917001）

详细信息

通讯作者:
齐会民，博士，教授，博士生导师，研究方向为耐高温树脂及复合材料　 E-mail: qihm@ecust.edu.cn

中图分类号: TB332
计量
- 文章访问数: 1254
- HTML全文浏览量: 289
- PDF下载量: 126
- 被引次数: 0
出版历程
- 收稿日期: 2020-02-10
- 录用日期: 2020-04-25
- 网络出版日期: 2020-05-07
- 刊出日期: 2020-12-15

Properties of cyanate ester resin for hot melt prepreg

HUO Xiaomeng^1
,,
WANG Fan^1
,,
YAO Zhuojun^2
,,
DAI Jingbin^2
,,
ZHU Yaping^1
,,
QI Huimin^{1
, ,}

1.
Key Laboratory of Specially Functional Polymeric Materials and Related Technology of Ministry of Education, School of Materials Science and Engineering, East China University of Science & Technology, Shanghai 200237, China
2.
Shanghai Composite Material & Technology Co. Ltd., Shanghai 200120, China

摘要

摘要: 采用聚醚砜(PES)对氰酸酯树脂改性，制备出PM915树脂。对PM915树脂的工艺性能和固化物性能进行了系统研究，该树脂成膜性和贮存稳定性良好，适用于热熔法预浸料工艺。研究了PM915树脂的流变性能及凝胶时间，树脂在70℃时的黏度为20 Pa·s左右，在120℃条件下可保持黏度稳定时间达115 min，160℃时凝胶时间为40 min。PM915树脂制备过程中部分反应热已释放，其拥有较低的固化放热焓，固化温度为220℃。通过引入热塑性组分PES，PM915树脂的固化收缩率低至0.16%。PM915树脂固化物具有优良的热性能，热失重5%时的温度T_d5=423℃，玻璃化转变温度T_g=276℃，热膨胀系数为4.4×10⁻⁵/℃。通过热塑性树脂的改性，引入了柔性基团，进而提高了树脂固化物的韧性，PM915树脂固化物的弯曲强度和弯曲模量分别为139.3 MPa和4.2 GPa，拉伸强度和拉伸模量分别为75.8 MPa和3.8 GPa；扫描电子显微镜（SEM）表征显示PM915树脂固化物为韧性断裂。结果表明，PM915树脂是一种适用于热熔法预浸料的氰酸酯树脂基体，且具有低固化收缩率、高尺寸稳定性和优良耐热性，可应用于卫星等航天器结构件。
- 氰酸酯树脂 /
- 热熔法 /
- 预浸料 /
- 流变性 /
- 耐热性
Abstract: PM915 resin was prepared by modifying cyanate ester resin with polyethersulfone (PES). The processability and cured resin properties of PM915 resin were investigated systematically. The PM915 resin has excellent process performance, good film-forming property and better storage stability, and could be used to prepare prepreg by hot melting method. The process properties such as rheological property and gel time of PM915 resin were measured. The results show that the viscosity of PM915 resin at 70℃ is about 20 Pa·s, the viscosity of the resin can keep stable for 115 min at 120℃, and the gelation time is 40 min at 160℃. Due to the release of some reaction heat in the preparation process, the curing exothermic enthalpy of PM915 resin decreases, and the curing temperature of PM915 resin is 220℃. The curing shrinkage of PM915 resin is as low as 0.16% due to the introduction of PES. The temperature at 5% thermal weight loss T_d5, glass transition temperature T_g and thermal expansion coefficient of cured PM915 resin are 423℃, 276℃ and 4.4×10⁻⁵/℃, respectively, which indicates that the cured PM915 resin possesses excellent thermal properties. After modification, the toughness of the cured resin has been greatly improved owing to the introduction of flexible groups. The flexural strength and modulus of the cured PM915 resin are 139.3 MPa and 4.2 GPa, the tensile strength and modulus of the cured PM915 resin are 75.8 MPa and 3.8 GPa respectively. What’s more, the investigation of fracture surface by scanning electron microscope (SEM) indicates that the cured PM915 resin exhibits toughness fracture. Therefore, the PM915 resin is a kind of ideal resin matrix for fiber reinforced prepregs by hot melting process, and possesses low curing shrinkage, high dimensional stability and heat resistance, which can be used in satellites and other spacecraft.
- cyanate ester resin /
- hot melt processing /
- prepreg /
- rheology /
- heat resistance

HTML全文

图 1 双酚A型氰酸酯单体(BACy)和聚醚砜(PES)的结构式

Figure 1. Structures of bisphenol A cyanate monomer (BACy) and polyethersulfone (PES)

下载: 全尺寸图片幻灯片

图 2 PES改性氰酸酯树脂(PM915树脂)的流变性能

Figure 2. Rheological properties of cyanate ester resin modified by PES (PM915) resin

下载: 全尺寸图片幻灯片

图 3 BACy及PM915树脂的DSC曲线

Figure 3. DSC curves of BACy and PM915 resin

下载: 全尺寸图片幻灯片

图 4 BACy-C和PM915-C的TGA曲线和DTG曲线

Figure 4. TGA and DTG curves of BACy-C and PM915-C

下载: 全尺寸图片幻灯片

图 5 BACy-C和PM915-C的DMA曲线

Figure 5. DMA curves of BACy-C and PM915-C

下载: 全尺寸图片幻灯片

图 6 PM915-C的热膨胀曲线

Figure 6. Thermal expansion curve of PM915-C

下载: 全尺寸图片幻灯片

图 7 BACy-C及PM915-C的介电性能

Figure 7. Dielectric properties of BACy-C and PM915-C

下载: 全尺寸图片幻灯片

图 8 PM915-C的断面形貌

Figure 8. Morphology of PM915-C

下载: 全尺寸图片幻灯片

表 1 PM915树脂凝胶时间

Table 1. Gelation time of PM915 resin

Sample	Gelation time t/min
Sample	130℃	140℃	150℃	160℃
PM915	151	115	75	40

下载: 导出CSV

表 2 BACy及PM915树脂的DSC数据

Table 2. DSC date of BACy and PM915 resin

Sample	T_i/℃	T_p/℃	T_f/℃	ΔH/(J·g^-1)
BACy	216.2	305.9	361.5	703.8
PM915	142.6	222.9	288.3	387.2
Notes: T_i, T_p and T_f —Initial curing temperature, peak curing temperature and final curing temperature, respectively; ΔH—Curing exothermic enthalpy.

下载: 导出CSV

表 3 BACy及PM915树脂的固化收缩率

Table 3. Shrinkage of BACy and PM915

Sample	ρ₁/(g·mL⁻¹)	ρ₂/(g·mL⁻¹)	V_s/%
BACy	1.208	1.234	2.11
PM915	1.218	1.220	0.16
Notes: ρ₁—Density of uncured resin; ρ₂—Density of cured resin; V_s—Cure shrinkage rate.

下载: 导出CSV

表 4 BACy-C及PM915-C的力学性能

Table 4. Mechanical properties of BACy-C and PM915-C

Property	BACy-C	PM915-C
Flexural strength/MPa	97.2	139.3
Flexural modulus/GPa	3.7	4.2
Tensile strength/MPa	−	75.8
Tensile modulus/GPa	−	3.8
Elongation/%	−	2.1

下载: 导出CSV

参考文献(27)

[1]	YUAN L, HUANG S, HU Y, et al. Poly(phenylene oxide) modified cyanate resin for self-healing[J]. Polymers for Advanced Technologies,2014,25:752-759. doi: 10.1002/pat.3290
[2]	ARAO Y, FUKUI T, NIWA T, et al. Dimensional stability of epoxy-based and cyanate-based carbon fiber-reinforced plastics[J]. Journal of Composite Materials,2015,49:1483-1492. doi: 10.1177/0021998314535455
[3]	刘锋, 周恒, 赵彤. 高性能树脂基体的最新研究进展[J]. 宇航材料工艺, 2012, 42:1-6. doi: 10.3969/j.issn.1007-2330.2012.03.001 LIU Feng, ZHOU Heng, ZHAO Tong. Progress of high-performance thermosetting resins[J]. Aerospace Materials & Technology,2012,42:1-6(in Chinese). doi: 10.3969/j.issn.1007-2330.2012.03.001
[4]	INAMDAR A, CHERUKATTU J, ANAND A, et al. Thermoplastic-toughened high-temperature cyanate esters and their application in advanced composites[J]. Industrial & Engineering Chemistry Research,2018,57:4479-4504.
[5]	宋健朗. 先进聚合物基结构复合材料在导弹和航天中的应用[J]. 工程塑料应用, 2008(7):50-54. doi: 10.3969/j.issn.1001-3539.2008.07.014 SONG Jianlang. Application of advanced polymer matrix composites in missle and aerospace[J]. Engineering Plastics Application,2008(7):50-54(in Chinese). doi: 10.3969/j.issn.1001-3539.2008.07.014
[6]	余训章. 高性能树脂基体在航空航天复合材料上的应用[J]. 玻璃钢, 2006(4):14-17. YU Xunzhang. The application of high performance resin on aeronautical and spacecraft composites[J]. Fiber Reinforced Plastics,2006(4):14-17(in Chinese).
[7]	GUAN Q B, GU A J, LIANG G Z, et al. Curing kinetics and mechanism of novel high performance hyperbranched polysiloxane/bismaleimide/cyanate ester resins for resin transfer molding[J]. Journal of Applied Polymer Science,2011,122:304-312. doi: 10.1002/app.34073
[8]	HE S B, LIANG G Z, YAN H X, et al. High performance toughened cyanate ester resin with low injection temperature for RTM process[J]. Polymers for Advanced Technologies,2009,20:143-146. doi: 10.1002/pat.1291
[9]	赵臻璐, 钟成, 黎昱, 等. POSS催化剂改性氰酸酯复合材料的性能[J]. 宇航材料工艺, 2014, 44:44-45, 49. doi: 10.3969/j.issn.1007-2330.2014.04.008 ZHAO Zhenlu, ZHONG Cheng, LI Yu, et al. Character of cyanate ester composite modified by POSS[J]. Aerospace Materials & Technology,2014,44:44-45, 49(in Chinese). doi: 10.3969/j.issn.1007-2330.2014.04.008
[10]	HAN B J, JEONG Y C, KIM C M, et al. Forming characteristics during the high-pressure resin transfer molding process for CFRP[J]. Advanced Composite Materials,2019,28:365-382. doi: 10.1080/09243046.2018.1556236
[11]	MAJI P, NEOGI S. Development of kinetics sub-model of cyanate ester-based prepregs for autoclave molding process simulation[J]. High Temperature Materials and Processes,2018(8):769-776.
[12]	FAINLEIB A, GRIGORYEVA O, VASHCHUK A, et al. Effect of ionic liquids on kinetic parameters of dicyanate ester polycyclotrimerization and on thermal and viscoelastic properties of resulting cyanate ester resins[J]. Express Polymer Letters,2019,13(5):469-483. doi: 10.3144/expresspolymlett.2019.39
[13]	田文平. 氰酸酯树脂改性及其碳纤维复合材料的性能研究[D]. 南京: 南京航空航天大学, 2016. TIAN Wenping. Study on properties of modified cyanate resin and its carbon fiber composites[D]. Nanjing: Nanjing University of Aeronautics and Astronautics, 2016(in Chinese).
[14]	韩成智, 张艺萌, 凌辉, 等. 热熔预浸料预浸工艺研究[J]. 玻璃钢/复合材料, 2014(5):59-63. doi: 10.3969/j.issn.1003-0999.2014.01.013 HAN Chengzhi, ZHANG Yimeng, LING Hui, et al. Study on the preimpregnation process of hot-melt prepreg[J]. Fiber Reinforced Plastics/Composites,2014(5):59-63(in Chinese). doi: 10.3969/j.issn.1003-0999.2014.01.013
[15]	徐燕, 李炜. 国内外预浸料制备方法[J]. 玻璃钢/复合材料, 2013(Z3):3-7. doi: 10.3969/j.issn.1003-0999.2013.01.001 XU Yan, LI Wei. Manufacturing methods of prepreg material[J]. Fiber Reinforced Plastics/Composites,2013(Z3):3-7(in Chinese). doi: 10.3969/j.issn.1003-0999.2013.01.001
[16]	王大伟, 林凤森, 黄海超. 适用于热熔法预浸料生产氰酸酯树脂的制备[J]. 化工新型材料, 2019, 47:233-234, 242. WANG Dawei, LIN Fengsen, HUANG Haichao. Preparation of cyanate resin for the production of melting prepared prepreg[J]. New Chemical Materials,2019,47:233-234, 242(in Chinese).
[17]	LI X D, ZHOU F, ZHENG T, et al. Blends of cyanate ester and phthalonitrile-polyhedral oligomeric silsesquioxane copolymers: Cure behavior and properties[J]. Polymers,2019,11(1):54.
[18]	姜雪, 刘锋, 雷子萱, 等. 热熔预浸工艺及热熔热固性树脂的研究进展[J]. 材料导报, 2017, 31:94-100. doi: 10.11896/j.issn.1005-023X.2017.04.021 JIANG Xue, LIU Feng, LEI Zixuan, et al. Advances in hot-melt thermosetting resin and its prepreg technology[J]. Materials Reports,2017,31:94-100(in Chinese). doi: 10.11896/j.issn.1005-023X.2017.04.021
[19]	王磊, 林娜, 潘玲英, 等. 新型改性氰酸酯及其复合材料性能[J]. 宇航材料工艺, 2012, 42:45-46, 50. doi: 10.3969/j.issn.1007-2330.2012.04.010 WANG Lei, LIN Na, PAN Lingying, et al. Performance of a new type of cyanate ester resin and composite materials[J]. Aerospace Materials & Technology,2012,42:45-46, 50(in Chinese). doi: 10.3969/j.issn.1007-2330.2012.04.010
[20]	CAI M C, YUAN Q L, HUANG F R. Catalytic effect of poly(silicon-containing arylacetylene) with terminal acetylene on the curing reaction and properties of a bisphenol A type cyanate ester[J]. Polymer International,2018,67:1563-1571. doi: 10.1002/pi.5679
[21]	杨依依, 王晓洁, 刘锋, 等. 氰酸酯MCE-085树脂固化行为和浇铸体性能研究[J]. 化工新型材料, 2018, 46:36-39. YANG Yiyi, WANG Xiaojie, LIU Feng, et al. Curing behavior and casting property of MCE-085 cyanate ester[J]. New Chemical Materials,2018,46:36-39(in Chinese).
[22]	中国国家标准化管理委员会. 树脂浇铸体性能试验方法: GB/T 2567—2008[S]. 北京: 中国标准出版社, 2009. Standardization Administration of the People’s Republic of China. Test methods for properties of resin casting body: GB/T 2567—2008[S]. Beijing: China Standards Press, 2009(in Chinese).
[23]	党凯. 高模碳纤维预浸料用氰酸酯树脂体系的研制[D]. 北京: 北京化工大学, 2017. DANG Kai. The research on cyanate ester resin system for high modulus carbon fiber prepreg[D]. Beijing: Beijing University Of Chemical Technology, 2017(in Chinese).
[24]	王冠. 液氧环境用改性氰酸酯树脂体系的制备与性能研究[D]. 哈尔滨: 哈尔滨工业大学, 2017. WANG Guan. Preparation and investigation of modified cyanate ester resin systems used in liquid oxygen[D]. Harbin: Harbin Institute of Technology, 2017(in Chinese).
[25]	黄智勇, 崔宝军, 陈维君, 等. 酚酞基聚芳醚砜改性双酚A型氰酸酯预聚体的制备及性能研究[J]. 化学与黏合, 2013, 35:22-26. HUANG Zhiyong, CUI Baojun, CHEN Weijun, et al. Preparation and study on the property of bisphenol A cyanate prepolymer modified with polyarylethersulfone with cardo group[J]. Chemistry and Adhesion,2013,35:22-26(in Chinese).
[26]	IIJIMA T, KATSURAYAMA S, FUKUDA W, et al. Modification of cyanate ester resin by poly(ethylene phthalate) and related copolyesters[J]. Journal of Applied Polymer Science,2000,76:208-219. doi: 10.1002/(SICI)1097-4628(20000411)76:2<208::AID-APP10>3.0.CO;2-N
[27]	颜红侠, 梁国正, 马晓燕, 等. 聚苯醚改性氰酸酯树脂的研究[J]. 西北工业大学学报, 2004, 22(3):301-303. doi: 10.3969/j.issn.1000-2758.2004.03.009 YAN Hongxia, LIANG Guozheng, MA Xiaoyan, et al. Study on cyanate ester resin modified with polyphenylene oxide[J]. Journal of Northwestern Polytechnical University,2004,22(3):301-303(in Chinese). doi: 10.3969/j.issn.1000-2758.2004.03.009